JP3368059B2 - Curable composition - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydroxyl group and / or a hydroxyl group.
It has a silicon atom to which a decomposable group is bonded, and has a siloxane bond
Having a silicon atom-containing group that can be cross-linked by forming
For a room temperature curable composition containing a saturated hydrocarbon polymer,
In particular, room temperature curing that provides cured products with excellent resilience
The present invention relates to an acidic composition. 2. Description of the Related Art At ambient temperature in the atmosphere, when exposed to moisture, it becomes rubbery.
Of hydroxyl groups and / or hydrolyzable groups
Having bonded silicon atoms to form siloxane bonds
Hydrocarbon having a silicon atom-containing group which can be crosslinked by
Elemental polymer (hereinafter referred to as “reactive silicon group-containing saturated hydrocarbon
"Polymer." ) Is a low-viscosity curable composition.
Handling because it is a thixotropic liquid composition
Easy, good storage stability,
No gas etc. is generated, the cured product has an appropriate viscoelastic strength,
Adhesives and special adhesives
Known as a sealing material for joints of buildings and transportation equipment
Have been. [0003] The reactive silicon group-containing saturated hydrocarbon is
The base polymer is used to connect elastic sealants for buildings and transportation equipment.
Used as a sealing material for joints to seal gaps (joints)
If it is injected, it is injected in liquid form when it is injected into the joint,
It cures to a rubber-like cured product. In this case, the cured product
Are required to have various properties, but among them,
After compression, the cured body is kept in a compressed state
The property of restoring the original state when the compression is released (restorability)
Is a characteristic particularly required to be good. [0004] Improve the resilience of the cured product of the above curable composition
, A divalent tin organic carboxylic acid as a curing catalyst
Salt and / or II-valent lead organic carboxylate, and optionally
Methods to use acidic substances or basic substances in combination depending on
However, it is still not enough and further improvement is desired.
Have been. SUMMARY OF THE INVENTION The object of the present invention is to
Has a high viscoelastic strength and produces a cured product with excellent adhesion.
Component containing reactive silicon group-containing saturated hydrocarbon polymer
In the mold-curable composition, in particular, excellent restorability and good
Room-temperature curability that produces a cured product that has both durability and workability
It is to provide a composition. [0006] The above objects of the present invention are as follows.
(A) a hydroxyl group or a hydrolyzable group bonded to a silicon atom
Can be crosslinked by forming siloxane bonds
Saturated hydrocarbon-based polymerization having at least one silicon-containing group
100 parts by weight of the body, and (B) charcoal having an average particle diameter of 1 μm or more
Calcium acid and (C) charcoal having an average particle size of 0.2 μm or less
100-200 parts by weight of calcium acid, (D)
40 to 150 parts by weight of plasticizer, (E) II-valent tin-based curing catalyst
0.5 to 10 parts by weight, and (F) an epoxy group-containing compound
2 to 40 parts by weight, and the above components (B) and (C)
(B) component accounts for 10 to 70% by weight in the total amount of
Curable composition in which the component (A) accounts for 15 to 35% by weight in the composition
This could be achieved by an adult. [0007] The above curable composition has poor workability and storage stability.
The strength, elongation and other properties required by the cured product.
Needless to say, they are satisfactory in terms of sex, etc.
No. Hereinafter, the present invention will be described in detail. In the present invention, water bonded to a silicon atom
Has an acid group or a hydrolyzable group and forms a siloxane bond
Silicon-containing groups that can be crosslinked by
Saturated hydrocarbon polymer having at least one silicon group (hereinafter referred to as a saturated hydrocarbon polymer)
Below, it is also called "saturated hydrocarbon polymer (A)". ) Used
Used. The reactive silicon group used in the present invention
Is a well-known functional group.
General formula (I): (Where R ¹ And R ^Two Has 1 to 20 carbon atoms
Alkyl group, aryl group having 6 to 20 carbon atoms, 7 to 7 carbon atoms
20 aralkyl groups, or (R ′) _Three SiO- (R '
Is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three
R ′ may be the same or different. )
R represents a triorganosiloxy group; ¹ And R ^Two Is two
When they exist, they are the same but different
You may. X represents a hydroxyl group or a hydrolyzable group;
When present they are the same but different
Is also good. a is 0, 1, 2 or 3, b is 0, 1 or
2, but a + mb ≧ 1. In addition, m number of [0010] B need not be the same. m is 0 or 1 to 1
It is an integer of 9. )).
You. As a hydrolyzable group in the general formula (1)
Is not particularly limited, and conventionally known hydrolysis
Groups, but specific examples include, for example, a hydrogen atom,
Lucoxy group, acyloxy group, ketoxime group,
Groups, amide groups, aminooxy groups, mercapto groups,
And a kenyloxy group. Of these, water content
Because of its mild dissolving power and easy handling,
Is particularly preferred. The hydrolyzable group and the hydroxyl group are one silicon atom.
Can be bound in the range of 1 to 3
b) preferably ranges from 1 to 5. Hydrolysable
When two or more groups or hydroxyl groups are bonded to the reactive silicon group
May be the same or different. The silicon atom forming the reactive silicon group is 1
May be used, or two or more.
In the case of silicon atoms connected by bonding or the like, 20
Is preferred. In particular, the formula: (Where R ^Two , X and a are the same as above. )
The reactive silicon group to be used is preferred because it is easily available. [0015] The reactive silicon group is a saturated hydrocarbon-based polymer.
At least one, preferably 1.1 to 5 per molecule of the body
Exists. One reactive silicon group in the molecule
If less, the curability becomes insufficient and the rubber elasticity is good.
It becomes difficult to exhibit behavior. [0016] The reactive silicon group may be a saturated hydrocarbon polymer.
May be present at the end of the body molecular chain,
Or both. Especially reactive silica
When a basic group is present at the terminal of the molecular chain,
Effectiveness of Saturated Hydrocarbon Polymer Component in Cured Product
High-strength, high-elongation rubber-like hardening due to increased amount of network chains
This is preferable in that the product can be easily obtained. Also these
Saturated hydrocarbon polymers having reactive silicon groups can be used alone.
Or two or more of them may be used in combination. The saturated hydrocarbon used in the present invention
The polymer substantially has carbon-carbon unsaturated bonds other than the aromatic ring.
Is a concept that means a polymer that does not contain an organic solvent.
Of Saturated Hydrocarbon Polymer Containing Reactive Silicon Group Used
The rated polymer can be obtained by the following method
Things. (1) Ethylene, propylene, 1-butene, a
An olefinic compound having 1 to 6 carbon atoms such as sobutylene
A method of polymerizing as a main monomer. (2) Diene compounds such as butadiene and isoprene are used alone
Polymerized or the above olefin compound and diene compound
And then hydrogenating. Among these polymers, a functional group is introduced at the terminal.
Easy to enter, easy to control molecular weight, large number of terminal functional groups
Isobutylene-based polymer and
It is preferably a hydrogenated polybutadiene polymer. The isobutylene-based polymer has a monomer unit
May be formed of isobutylene units.
Isobutylene monomer units copolymerizable with sobutylene
50% (wt%, the same applies hereinafter) in the polymer
Or less, more preferably 30% or less, particularly preferably 10% or less.
% Or less. Examples of such a monomer component include, for example,
C4-12 olefins, vinyl ethers, aromatics
Vinyl compounds, vinylsilanes, allylsilanes, etc.
I can do it. Specific examples of such a copolymer component include:
For example, 1-butene, 2-butene, 2-methyl-1-butene, 3-
Methyl-1-butene, pentene, 4-methyl-1-pentene,
Hexene, vinylcyclohexane, methyl vinyl ether
, Ethyl vinyl ether, isobutyl vinyl ether
Styrene, α-methylstyrene, dimethylstyrene
, Monochlorostyrene, dichlorostyrene, β-pine
, Indene, vinyltrichlorosilane, vinylmethyl
Dichlorosilane, vinyldimethylchlorosilane, vinyl
Dimethylmethoxysilane, vinyltrimethylsilane, di
Vinyl dichlorosilane, divinyl dimethoxy silane, di
Vinyldimethylsilane, 1,3-divinyl-1,1,3,3-tetra
Methyldisiloxane, trivinylmethylsilane, tetra
Vinylsilane, allyltrichlorosilane, allylmethyl
Dichlorosilane, allyldimethylchlorosilane, allyl
Dimethylmethoxysilane, allyltrimethylsilane, di
Allyl dichlorosilane, diallyldimethoxysilane, di
Allyldimethylsilane, γ-methacryloyloxypro
Piltrimethoxysilane, γ-methacryloyloxyp
And propylmethyldimethoxysilane. [0022] Monomers copolymerizable with these isobutylenes
When vinyl silanes or allyl silanes are used as
The silicon content of the coalesce increases, making it a silane coupling agent.
The number of groups that can act and increase the adhesiveness of the resulting composition
Is improved. Furthermore, hydrogenated polybutadiene-based polymers and other
Even in saturated hydrocarbon polymers, isobutylene-based
As in the case of the body, in addition to the main monomer unit, other
A monomer unit may be contained. Also, the saturated hydrocarbon polymerization used in the present invention
In the body, butadiene as long as the object of the present invention is achieved,
Double bonding after polymerization such as polyene compounds such as isoprene
A small amount of the remaining monomer units, preferably 10% or less,
May be contained in a range of 5% or less, particularly 1% or less.
No. The saturated hydrocarbon polymer (A), especially
Number of sobutylene polymers and hydrogenated polybutadiene polymers
The average molecular weight should be around 500-100,000
Preferred, especially about 1,000 to 30,000 liquids
It is preferable to use the most fluid because it is easy to handle.
No. Furthermore, the molecular weight distribution (M _w / M _n ) Is the same
M in terms of lower viscosity at molecular weight _w / M _n But
The narrower the better. The above saturated hydrocarbon group having a reactive silicon group
Regarding the method for producing a polymer, particularly, an isobutylene-based polymer
And the case of hydrogenated polybutadiene polymer as an example
Will be described. The above-mentioned isobutylene having a reactive silicon group
Isomers having a reactive silicon group at the molecular terminal
Butylene polymer is a polymerization method called the inifer method.
(Uses both initiator and chain transfer agent called inifer
Terminal obtained by a cationic polymerization method using a specific compound)
Functional, preferably all-terminal functional isobutylene polymer
Can be manufactured. Such a manufacturing method
JP-A-63-6003, 63-6041, 63
-254149, 64-38407, 64-2
It is described in each specification of No. 2904 and the like. In addition, a compound having a reactive silicon group in the molecule
Sobutylene-based polymer is a monomer containing mainly isobutylene
Vinyl silanes or allyls containing reactive silicon groups in the body
Manufactured by adding silanes and copolymerizing
You. Further, a compound having a reactive silicon group at a molecular terminal
In the polymerization for producing sobutylene-based polymer,
It has a reactive silicon group other than the component isobutylene monomer.
Vinyl silanes and allyl silanes
Later, by introducing a reactive silicon group to the terminal,
And isobutylene system having a reactive silicon group inside the molecular chain
Polymers can be produced. Vinyl silanes having a reactive silicon group
And specific examples of allylsilanes, for example, vinyl
Trichlorosilane, vinylmethyldichlorosilane, vinyl
Dimethyl chlorosilane, vinyl dimethyl methoxy sila
, Divinyldichlorosilane, divinyldimethoxysila
, Allyltrichlorosilane, allylmethyldichlorosilane
Orchid, allyldimethylchlorosilane, allyldimethylme
Toxysilane, diallyldichlorosilane, diallyldimethyl
Toxysilane, γ-methacryloyloxypropyl tri
Methoxysilane, γ-methacryloyloxypropyl
Tildimethoxysilane and the like. Process for producing the above hydrogenated polybutadiene polymer
For example, for example, first,
The hydroxyl group of the tadiene-based polymer is converted to an oxy group such as -ONa or -OK.
After conversion to a simetal group, the general formula (2): CH _Two = CH-R ^Three —Y (2) (wherein, Y is a halogen atom such as a chlorine atom, an iodine atom, etc.)
R ^Three Is -R ^Four -, -R ^Four -OC (= O)-, -R
^Four -C (= O)-(R ^Four Is a divalent carbon having 1 to 20 carbon atoms
Preferred examples of the hydrogen group include an alkylene group and a cycloalkyl group.
Loalkylene group, arylene group, aralkylene group
Is a divalent organic group represented by the formula _Two -And
R "-Ph-CH _Two -(R ″ is a hydrocarbon having 1 to 10 carbon atoms)
An element group, Ph, is a p-phenylene group. 2) selected from
Valent groups are particularly preferred. ) Organic halogen compounds
Having a terminal olefin group by reacting
Hydrogenated polybutadiene polymer (hereinafter referred to as olefin-terminated water)
Polybutadiene polymer).
it can. Hydroxy-terminated polybutadiene-based polymerization
As a method of converting the terminal hydroxyl group of the body into an oxymetal group,
Alkali metals such as Na and K; Metal water such as NaH
Hydride; NaOCH _Three Metal alkoxides such as
Method to react with caustic alkalis such as OH and KOH
Can be mentioned. In the above method, the starting material
Was approximately the same as the hydroxy-terminated polybutadiene polymer
Hydrogenated polybutadiene system with terminal olefin having the same molecular weight
A polymer is obtained, but to obtain a higher molecular weight polymer
Is reacted with an organic halogen compound of the general formula (2).
Before, methylene chloride, bis (chloromethyl) benzene,
Halogen in one molecule such as bis (chloromethyl) ether
Reacting with a polyvalent organic halogen compound containing two or more atoms
After increasing the molecular weight by an organic compound represented by the general formula (2)
When reacted with halogen compounds, higher molecular weight, terminal
A hydrogenated polybutadiene polymer having an olefin group
Obtainable. An organic halogen represented by the general formula (2)
Specific examples of the compound include allyl chloride and allyl chloride.
Lomide, vinyl (chloromethyl) benzene, allyl
(Chloromethyl) benzene, allyl (bromomethyl) benzene
Benzene, allyl (chloromethyl) ether, allyl
(Rolomethoxy) benzene, 1-butenyl (chloromethyl)
Ether, 1-hexenyl (chloromethoxy) benzene,
Allyloxy (chloromethyl) benzene, etc.
However, the present invention is not limited to these. Of these,
Allyl chloride is inexpensive and easily reacts.
preferable. Hydrogenated polybutadiene-based polymerization of terminal olefin
The reactive silicon group is introduced into the body by adding reactive silicon
As in the case of the isobutylene polymer having a group,
For example, a hydrogen atom is bonded to a group represented by the general formula (1).
Hydrosilane compound, preferably of the general formula: (Where R ^Two , X and a are the same as above. )
Of the compound to be added using a platinum-based catalyst
Can be manufactured more. A hydrogen atom is added to the group represented by the general formula (1).
Specific examples of the hydrosilane compound bonded with
For example, trichlorosilane, methyldichlorosilane, dimethyl
Halogen such as ruchlorosilane and phenyldichlorosilane
Silanes: trimethoxysilane, triethoxysila
, Methyldiethoxysilane, methyldimethoxysila
, Alkoxysilanes such as phenyldimethoxysilane
: Methyldiacetoxysilane, phenyldiacetoxy
Acyloxysilanes such as silane; bis (dimethylketoki)
(Simate) methylsilane, bis (cyclohexyl ketoki)
Ketoximate silanes such as shimate) methyl silane
But are not limited to these. This
Of these, halogenated silanes, alkoxysila
Are preferred. In the present invention, as the component (B), a particle size
Use calcium carbonate of 1 μm or more. Such carbonic acid
The use of calcium improves the resilience of the cured product.
Be improved. The average particle size of the component (B) calcium carbonate and
Is preferably 1 to 5 μm, and the above calcium carbonate
May be surface-treated with a fatty acid or the like. the above
(B) Heavy calcium carbonate is used as calcium carbonate
Calcium carbonate, for example, Sandra
Site ^# 100, ^# 300 (or more, manufactured by Takehara Chemical Industries), N
S ^# 100, ^# 200, ^# 400, ^# 600, ^# 1000,
NN ^# 500, SS80 (all manufactured by Nitto Powder Co., Ltd.),
EC-1, 5, MC coat P-13, S-13, snow
Light SS, SSS, M White, Super ^# 150
0, ^# 1700, ^# 2000, ^# 2300 (or more, Maruo
Lucium), Whiten SB, P-10, 20, 3
0, 40, 50 (all of which are manufactured by Shiraishi Calcium)
It can be listed as being. In the present invention, as the component (C), an average
Use calcium carbonate having a particle size of 0.2 μm or less. this
By using such calcium carbonate,
It is possible to obtain a curable composition free from defects. Average particle
The diameter is preferably from 0.01 to 0.15 μm. Ma
Organic substances such as fatty acids, resin acids, and lignin, particularly fatty acids
Calcium carbonate surface-treated with is preferred. (C) As the calcium carbonate as the component
Is white luster flower O, Karmos, white luster flower CC, white luster flower CCR,
Listed are those sold under the trade name of VIGOT-15 etc.
I can do it. The calcium carbonate is combined with the component (B).
100 to 200 parts by weight in total with the above component (C)
Use within the range. Composition if less than 100 parts by weight
It is difficult to control the viscosity of objects, which is economically disadvantageous
Is not preferred. If it exceeds 200 parts by weight, the composition
The viscosity of the material is too high, which reduces workability and durability
This is not preferred because the properties are also reduced. The sum of the components (B) and (C)
The component (B) in the amount is 10 to 70% by weight, preferably
It needs to be present at 20 to 60% by weight. The ratio is 1
If the amount is less than 0% by weight, the restoring force of the cured product is not sufficient, which is preferable.
If more than 70% by weight, sagging etc. will occur during work
The composition is not preferred. In the present invention, the component (D)
As the plasticizer, for example, dioctyl phthalate, dib
Such as tyl phthalate and butyl benzyl phthalate
Phthalates; dioctyl adipate, succinic acid
Aliphatic disalts such as isodecyl and dibutyl sebacate
Base acid esters: diethylene glycol dibenzoate
Glyco such as pentaerythritol ester
Esters; butyl oleate, acetyl ricinol
Aliphatic esters such as methyl phosphate;
Jill, trioctyl phosphate, octyl diphenyl phosphate
Phosphate esters such as epoxidized soybean oil, Epo
Xylated linseed oil, benzyl epoxy stearate, etc.
Epoxy plasticizers such as dibasic acids and dihydric alcohols
Polyester plasticizers such as polyesters; Polypropylene
Polyethers such as pyrene glycol and derivatives thereof;
Polices such as poly-α-methylstyrene and polystyrene
Tylenes: polybutadiene, butadiene-acrylonite
Ryl copolymer, polychloroprene, polyisoprene, poly
Libutene, chlorinated paraffins, petroleum softeners, alk
One or more plasticizers such as benzene-based plasticizers
Can optionally be used in the form of a mixture of However, good
More preferably, it is necessary to select one having good compatibility. In the present invention, the component (D) is
It is necessary to use 40 to 150 parts by weight of the agent. Use
If the dose is less than 40 parts by weight, the viscosity of the composition becomes too high.
Excessive workability such as extrusion
No. If the amount exceeds 150 parts by weight, the plasticizer bleeds over time
Large changes in physical properties and when paint is applied to the surface
Moreover, it is not preferable because the quality of the paint is deteriorated. In the present invention, II as the component (E)
Valent Tin-Based Curing Catalyst Affects Both Curing Speed and Durability Properties
Important compounding agents, such as tin octylate and lauric acid
Tin, tin ferzaticate and the like can be exemplified, but especially octyl
Tin acid is preferred. The use amount of the above-mentioned II-valent tin-based curing catalyst is as follows:
It is necessary to use 0.5 to 10 parts by weight. amount to use
Is less than 0.5 parts by weight, the curing speed is too slow,
It is not preferable because it causes a problem. If it exceeds 10 parts by weight,
Adversely affects durability, especially repeated fatigue characteristics and resilience
Therefore, it is not preferable. The curing rate of a tin-based tin-based curing catalyst alone is
If not, use amine compounds as co-catalysts.
Can be used. As the amine compound, for example,
Diethylenetriamine, triethylenetetramine, tet
Laethylenepentamine, butylamine, hexylami
Octylamine, decylamine, laurylamine,
Hexamethylenediamine, triethanolamine, dib
Tylamine, diethanolamine, N, N, N ', N'
-Tetramethyl-1,3-butanediamine, benzyla
Min, cyclohexylamine, dodecamethylene diami
, Dimethylethylenediamine, dimethylaminoethanol
, N, N, N ', N'-tetramethylethylenedia
Min, triethylamine, N, N-dimethylaniline,
Dimethylbenzylaniline and the like.
Primary amines are preferred from the viewpoint of ease of handling, and
Urylamine is particularly preferred. In the composition of the present invention, the resilience is enhanced.
Therefore, an epoxy group is contained in one molecule as the component (F).
The compound used is Specific examples of the compound include
Poxylated unsaturated oils and fats, epoxidized unsaturated fatty acid esters
Compounds, alicyclic epoxy compounds, epichlorohydrin
Examples of the compound shown in the conductor and mixtures thereof are given.
Specifically, for example, epoxidized soybean oil, epoxidized
Oil, di- (2-ethylhexyl) -4,5-epoxy
Cycyclohexane-1,2-dicarboxylate (E-
PS), epoxy octyl stearate, epoxy dib
Chill stearate and the like. In the composition of the present invention, other than calcium carbonate
It is also possible to use other fillers in combination. Can be used together
Such fillers include, for example, fumed silica, sedimentable
Silica, silicic anhydride, hydrous silicic acid, carbon black, carbonic acid
Magnesium, diatomaceous earth, calcined clay, clay, tall
, Titanium oxide, bentonite, organic bentonite, acid
Ferric chloride, zinc oxide, activated zinc flower, shirasu balloon, stone
Cotton and glass fiber can be mentioned. In the present invention, the composition is provided with thixotropic properties.
For imparting, various thixotropic agents can be added.
As the thixotropic agent, hydrogenated castor oil, amide wax,
Aluminum stearate, calcium stearate,
Zinc stearate, fine powder silica, organic bentonite
Among them, hydrogenated castor oil is a specialty.
Preferred. 0.5-7 parts by weight of hydrogenated castor oil
It is preferable to use in the range. In the present invention, durability, especially surface weather resistance
UV absorbers can be used to enhance the properties
You. Examples of the ultraviolet absorber include benzophenone
System, benzotriazole system, salicylate system, substituted tri
And metal chelate compounds.
Of these, benzotriazoles are particularly preferred.
Good. For the same purpose, in the present invention, an antioxidant is used.
It is also effective to use. Examples of the antioxidant include:
For example, hindered phenolic, monophenolic,
Sphenolic and polyphenolic compounds
, But especially hindered phenols
Are preferred. Similarly, in the present invention, for example,
Bin 622LD, Tinuvin 144, CHIMASSORB944LD, CHIMA
SSORB119FL (All of these are Nippon Ciba Geigy Co., Ltd.
MARK LA-57, MARK LA-62, MARK LA-67, MARK LA-
63, MARK LA-68 (all of which are Adeka Argus Chemical shares)
Sanol LS-770, Sanol LS-765, Sanol
LS-292, Sanol LS-2626, Sanol LS-1114, Sanoh
Le LS-744 (both manufactured by Sankyo Co., Ltd.)
Hindered amine light stabilizers can be used
You. In the present invention, at least one molecule
Compounds containing two or more acrylic or methacrylic functional groups
It is also effective to add a compound to increase the surface weather resistance.
is there. Specifically, the compounds shown below, for example, specialty
Acrylic (bifunctional) Aronix M-210, Alonix
Kusu M-215, Aronix M-220, Aronix M-233
, Aronix M-240, Aronix M-245;
Acrylic (trifunctional) Aronix M-305, Alonix
Kusu M-309, Aronix M-310, Aronix M-315
, Aronix M-320, Aronix M-325;
Aronix M-400 (particularly polyacrylate)
Aronix is manufactured by Toagosei Chemical Industry Co., Ltd.)
And the like.
Compounds are preferable, and three compounds are averaged in one molecule.
Compounds containing the above acrylic functional groups are preferred. The compound is used in the range of 0.5 to 10 parts by weight.
And less than 0.5 parts by weight enhances weather resistance.
No effect. If more than 10 parts by weight, the cured product becomes too hard
Therefore, it is not preferable because cracks occur. The composition of the present invention thus obtained
Is waterproofing, sealing agent, adhesive, adhesive, paint, paint film
Agent, sealant composition, molding material, cast rubber material, foam
It can be usefully used as a material. EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples.
However, the present invention is not limited to these. Production Example 1 A four-necked flask was equipped with a stirrer and a nitrogen line.
In this, 560 ml of dry methylene chloride, n-hexane
1160 ml of sun, 940 mg of α-methylpyridine, p
-22 g of dicumyl chloride is weighed to obtain a homogeneous mixed solution.
After cooling to -70 ° C, isobutylene mono
570 ml of mer is charged through a Molecula sieve tube
It is. In the reaction solution cooled to -70 ° C,
Under stirring, the polymerization catalyst solution (titanium tetrachloride 14
ml / 80 ml of methylene chloride) at once.
Started. Once heated to -54 ° C, it takes about 17 minutes
The temperature was lowered to -70 ° C. About 20 minutes after the start of the polymerization, 1,9-decadiene
132 g of ene was added, and the mixture was further stirred at -70 ° C for 4 hours.
Continued. The yellow-colored reaction solution was added to 3 L of warm water (about 45 L).
C), stirred for about 2 hours, separated the organic layer,
Was repeated three times. The thus obtained colorless and transparent organic layer is decompressed.
Concentrated, isobutylene oligo having vinyl groups at both ends
About 400 g of the mer was obtained. Next, the vinyl thus obtained
400 g of the group-containing isobutylene oligomer was added to n-hepta
Dissolved in 200 ml of solution and heated to about 70 ° C.
Ludimethoxysilane 1.5 [eq / vinyl group], platinum
(Vinylsiloxane) complex 1 × 10 ^-Four [Eq / vinyl
And a hydrosilylation reaction was carried out. FT-I
Follow the reaction by R, 1640cm in about 4 hours ^-1 of
Olefin absorption disappeared. By concentrating the reaction solution under reduced pressure,
Having a reactive silicon group at both ends and a molecular weight of 5300
An isobutylene oligomer was obtained. [Structural formula] Examples 1 to 7 and Comparative Examples 1 to 7 With respect to 100 parts by weight of the polymer obtained in Production Example 1,
-1 and Table 2 at the mixing ratio (parts by weight) shown in Tables 1 and 2.
And compounding agents of components (B) to (F) shown in Table-2
Thus, a curable composition was prepared. The composition and the cured product were evaluated for workability and recovery.
Properties and weather resistance are measured and evaluated by the following test methods.
Valued. The results are shown in Tables 1 and 2 below. In the table
The method for evaluating the characteristics of is as follows. * 1 Workability: Extrusion from cartridge
Measures properties and spatula breakability. * 2 Restorability: JIS-type cured product at 90 ° C, 30% for 7 days
Compress and measure the resilience one day after decompression. * 3 Sunshine weather meter weather resistance
Test: Suga Test Machine Sunshine Weather Meter Test
Irradiates the surface of the cured product sheet with a test machine and cracks occur
Measure the irradiation time until. [Table 1] [Table 2] It is clear from the results of Tables 1 and 2 above that
As described above, the composition of the present invention comprises the components (B) to (F).
Recoverability, workability and weather resistance by containing everything
Can be said to be effective in all respects
You. The curable composition of the present invention has particularly excellent reversion.
With good durability and good workability for strength and elongation
To give excellent cured products.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-5-287187 (JP, A) JP-A-2-185565 (JP, A) JP-A-2-97562 (JP, A) JP-A-1- 252670 (JP, A) JP-A-1-16864 (JP, A) JP-A-1-167371 (JP, A) JP-A-1-170658 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 1/00-101/16 C08K 3/00-13/08

Claims (1)

(A) Claims 1. (A) It has a hydroxyl group or a hydrolyzable group bonded to a silicon atom, and has at least one silicon-containing group which can be crosslinked by forming a siloxane bond. 100 parts by weight of a saturated hydrocarbon polymer, (B) calcium carbonate having an average particle diameter of 1 μm or more, and (C) an average particle diameter of 0.1 μm.
100 to 200 parts by weight of a total of 2 μm or less of calcium carbonate, (D) 40 to 150 parts by weight of a plasticizer, (E) 0.5 to 10 parts by weight of a tin-based curing catalyst having a valence of II, and (F) containing an epoxy group. 2 to 40 parts by weight of the compound (B)
The component (B) accounts for 10 to 70% by weight in the total amount of the components and the component (C), and the component (A) accounts for 15 to 35% by weight in the total composition.
A curable composition characterized by comprising: